Aromatic polyepoxide treated derivatives of alkylene oxide-amine modified phenolic-resins, and method of making same



AROMATIC PQLYEPOXWE TREATED DERIVA- TIVES F ALKYLENE ()XIDE-AMINEMQDIFTED PIENOLllC-RESINS, AND METHOD OF MAKING SAME Melvin De Groote,St. Louis, and Kwan-Ting Shen, Brentwood, Mo., assignors to PetroliteCorporation, Wilmington, DeL, a corporation of Delaware No Drawing.Original application April 22, 1953, Serial No. 350,533, now Patent No.2,771,432, dated November 20, 1956. Divided and this application June15, 1956, Serial No. 591,555

4 Claims. (Cl. zap-4s The present invention is a division of ourcopending application Serial No. 350,533, filed April 22, 1953.

Our invention is concerned with new chemical products or compoundsuseful as demulsifying agents in processes or procedures particularlyadapted for preventing, breaking or resolving emulsions of thewater-in-oil type and particularly petroleum emulsions. Our invention isalso concerned with the application of such chemical products orcompounds in various other arts and industries as well as with methodsof manufacturing the new chemical products or compounds which are ofoutstanding value in demulsification.

Attention is directed to two co-pending De Groote applications, SerialNo. 310,553, filed September 19, 1952, and Serial No. 333,389, filedJanuary 26, 1953. These two applications described hydrophile productsobtained by the oxyalkylation of the condensation product of certainphenol-aldehyde resins with respect to non-hydroxylated polyamines andformaldehyde.

The present invention is concerned with a method of reacting saidoxyalkylated derivatives of the kind just described with a phenolicpolyepoxide of the kind previously described in our aforementionedco-pending application, Serial No. 305,079.

Thus the present invention is concerned with products of reactionobtained by a 3-step manufacturing process involving (1) condensingcertain phenol aldehyde resins, hereinafter described in detail, withcertain basis nonhydroxylated polyamines, hereinafter described indetail, and formaldehyde; (2) oxyalkylation of the condensation productwith certain monoepoxides, hereinafter described in detail; and (3)oxyalkylation of the previously oxyalkylated resin condensate withcertain phenolic polyepoxides, hereinafter described in detail, andcogenerical- 1y associated compounds formed in their preparation.

A more limited aspect of the present invention is concerned withproducts of reaction wherein the oxyalkylated resin condensate isreacted with a member of the class of compounds of the following formula2 l Hz in which R represents a divalent radical including ketoneresidues formed by the elimination of the ketonic oxygen atom andaldehyde residues obtained by the elimination of the aldehydic oxygenatom; the divalent radical the divalent radical, the divalent sulfoneradical, and the divalent monosulfide radical S, the divalent radical.nite States atent O might be not only insoluble but also infusible.

"ice

2 and the divalent disulfide radical S-S; and R 0 is the divalentradical obtained by the elimination of a hydroxyl hydrogen atom and anuclear hydrogen atom from the phenol in which R, R", and R" representhydrogen and hydrocarbon substituents of the aromatic nucleus, saidsubstituent member having not over 18 carbon atoms.

A further limited aspect of the invention is represented by the productswherein the oxyalkylated resin condensate is reacted with a member ofthe class of (a) compounds of the following formula:

wherein R is essentially an aliphatic hydrocarbon bridge, each nindependently has one of the values 0 tol, and R is an alkyl radicalcontaining from 1 to 4 carbon atoms, or even 12 carbon atoms, and (b)cogenerically associated compounds formed in the preparation of (a)preceding, includingmonoepoxides.

Reference herein to being thermoplastic or non-thermosettingcharacterizes products as being liquids at ordinary temperature orreadily convertible to liquids by merely heating below the point ofpyrolysis and thus differentiates them from infusible resins. Referenceto being soluble in an organic solvent means any of the usual organicsolvents, such as alcohols, ketones, esters, ethers, mixed solvents,etc. Reference to solubility is merely to differentiate from a reactantwhich is not soluble and Furthermore, solubility is a factor insofarthat it is sometimes desirable to dilute the compound containing theepoxy rings before reacting with the monoepoxide-derived product. Insuch instances, of course, the solvent selected would have to be onewhich is not susceptible to oxyalkylation, as for example, kerosene,benzene, toluene, dioxane, various ketones, chlorinate solvents, dibutylether, dihexyl ether, ethyleneglycol diethylether, diethylenegiycoldiethylether, and dimethoxytetraethyleneglycol.

The expression epoxy is not usually limited to the l,2-epoxy ring. The1,2-epoxy ring is sometimes referred to as the oxirane ring todistinguish it from other epoxy rings. Hereinafter the word epoxy unlessindicated otherwise, will be used to mean the oxirane ring, i. e., the1,2-epoxy ring. Furthermore, where a compound has two or more oxiranerings theywill be referred to as polyepoxides. They usually represent,of course, 1,2- epoxy rings or oxirane rings in the alpha-omegaposition. This is a departure, of course, from the standpoint ofstrictly formal nomenclature as in the example of the simplest diepoxidewhich contains at least 4 carbon atoms and is formally described asl,2-epoxy-3,4-epoxybutane- (l,2-3,4 diepoxybutane).

It well may be that even though the previously suggested formularepresents the principal component, or components, of the resultant orreaction product described 0 in the previous text, it may be importantto note that 3 resinous epoxides which are polyether derivatives ofpolyhydric phenols containing an average of more than one epoxide groupper molecule and free from functional groups other than epoxideand'hydroxyl groups. See

the basicity of any nitrogen group is obviously diminished.

The polyepoxide-treated condensates obtained in the manner describedare, in turn, oxyalkylation-susceptible U. S. Patent No. 2,494,295,dated January 19, 1950, to 5 and valuable derivatives can be obtained byfurther re- Greenlee. The compounds here included are limited to actionwith ethylene oxide, propylene oxide, ethylene the monomers or the lowmolal members of such series imine, etc. and generally contain twoepoxide rings per molecule Similarly, the polyepoxide-derived compoundscan be and may be entirely free from a hydroxy group. This reacted witha product having both a nitrogen group is important because the instantinvention is directed toand a 1,2-epoxy group, such as 3dialkylaminoepoxywards products which are not insoluble resins and havepropane. See U. S. Patent No. 2,520,093, dated August certain solubilitycharacteristics not inherent in the usual 22, 1950, to Gross.thermosetting resins. Although the herein described products have a num-Having obtained a reactant having generally 2 epoxy ber of industrialapplications, they are of particular value rings as depicted in the lastformula preceding, or low for resolving petroleum emulsions of thewater-in-oil type molal polymers thereof, it becomes obvious thereaction that are commonly referred to as cut oil, roily oil," can takeplace with any oxyalkylated phenol-aldehyde emulsified oil, etc., andwhich comprise fine droplets resin by virtue of the fact that there arealways present of naturally-occurring waters or brines dispersed in aeither phenolic hydroxyl radicals or alkanol radicals remore or lesspermanentstate throughout the oil which sulting from the oxyalkylationofthe phenolic hydroxyl constitutes the continuous phase of the emulsion.radicals; there may be present reactive hydrogen atoms The new productsare useful as wetting, detergent and attached to a nitrogen atom or anoxygen atom, dependleveling agents in the laundry, textile and dyeingining on whether initially there was present a hydroxylated dustries; aswetting agents and detergents in the acid group attached to an aminohydrogen group or a secwashing of building stone and brick; as wettingagents ondary amino group. In any event there is always a and Spreadersin the application of asphalt in road buildmultiplicity of reactivehydrogen atoms present in the ing and the like; as a flotation reagentin the flotation oxyalkylated amine-modified phenol-aldehyde resin.separation of various aqueous suspensions containing To illustrate theproducts which represent the subject negatively charged particles, suchas sewage, coal washmatter of the present invention reference will bemade ing waste water, and various trade wastes and the like; to areaction involving a mole of the oxyalkylating agent, as gcrmicides,insecticides, emulsifying agents, as, for i. e., the compound having twooxirane rings and an example for cosmetics, spray oils, water-repellenttextile oxyalkylated amine condensate. Proceeding with the exfinishes;as lubricants, etc. ample previously described it is obvious thereaction For purpose of resolution of petroleum emulsions of ratio oftwo moles of the oxyalkylated amine condensate the water-in-oil type, weparticularly prefer to use those to one mole of the oxyalkylating agentgives a product products which as such or in the form of the free basewhich may be indicated as follows: or hydrate, i. e., combination withwater or particularly Oxyalkylated condensate) (Oxyalkylated eondensate) in which the various characters have their previous sigin theform of a low molal organic acid salt such as the nificance and thecharacterization oxyalkylated condengluconates or the acetate or hydroxyacetate, have sutfisate is simply an abbreviation for the oxyalkylatedconciently hydrophile character to at least meet the test set densatewhich is described in greater detail subsequentforth in U. S. Patent No.2,499,368, dated March 7, Y- 1950, to De Groote et al. In said patentsuch test for Such final product in turn also must be soluble butemulsification using a water-insoluble solvent, generally solubility isnot limited to an organic solvent but may xylene, is described as anindex of surface activity. include water, or for that matter, a solutionof water In the present instance the various condensation prodcontainingan acid such as hydrochloric acid, acetic acid, ucts as such or in theform of the free base or in the hydroxyacetic acid, etc. In other words,the nitrogen form of the acetate, may not necessarily be xylene-solublegroups present, whether four or more, may or may not although they arein many instances. If such compounds be significantly basic and it isimmaterial whether aqueous are not xylene-soluble the obvious chemicalequivalent solubility represents an anhydro base or the free base orequivalent chemical test can be made by simply using (combination withwater) or a salt form such as the some suitable solvent, preferably awater-soluble solvent acetate, chloride, etc. The purpose in thisinstance is such as ethylene glycol diethylether, or a low molal todifferentiate from insoluble resinous materials, paralcohol, or amixture to dissolve the appropriate prodticularly those resulting fromgelation or cross-linking. uct being examined and then mix with theequal weight Not only does this property serve to differentiate fromof'xylene, followed by addition of water. Such test is instances wherean insoluble material is desired, but also obviously the same for thereason that there will be serves to emphasize the fact that in manyinstances the two phases on vigorous shaking and surface activitypreferred compounds have distinct water-solubility or are makes itspresence manifest. It is understood the referdlstinctly dispersible in5% gluconic acid. For instance, ence in the hereto appended claims as tothe use of the products freed from any solvent can be shaken with xylenein the emulsification test includes such obvious 5 to 20 times theirweight of 5% gluconic acid at ordinary variant. temperature and show atleast some tendency towards For purpose of convenience, what is saidhereinafter betngself-dispersing. The solvent which is generally will bedivided into ten parts with Part 3, in turn, being tr ed 1s xylene. Ifxylene alone does not serve then a divided into three subdivisions:m1xture of xylene and methanol, for instance, 80 parts Part 1 isconcerned with our preference in regard to of xylene and 20 parts ofmethanol, or 70 parts of xylene the polyepoxide and particularly thediepoxide reactant; and 30 parts of methanol, can be used. Sometimes itis Part 2 is concerned with certain theoretical aspects desirable to adda small amount of acetone to the of diepoxide preparation;Xylene-methanol mixture, for instance, 5% to 10% of Part 3, SubdivisionA, is concerned with the preparaacetone. -As oxyalkylation proceeds thesignificance of tion of monomeric diepoxides, including Table I;

Part 3, Subdivision B, is concerned with the preparation of low molalpolymeric epoxides or mixtures containing low molal polymeric epoxidesas well as the monomer and includes Table II;

Part 3, Subdivision C, is concerned with miscellaneous phenolicreactants suitable for diepoxide preparation;

Part 4 is concerned with the phenol-aldehyde resin which is subjected tomodification by condensation reaction to yield an amine-modified resin;

Part 5 is concerned with basic nonhydroxylated polyamines having atleast one secondary amino group and having not over 32 carbon atoms inany radical attached to any amino nitrogen atom, and with the furtherproviso that the polyamine be free from any primary amino radical, anysubstituted imidazoline radical, and any substitutedtetrahydropyrimidine radical; and

Part 6 is concerned with reactions involving the resin, the amine, andformaldehyde to produce specific products or compounds which are thensubjected to oxyalkylation with monoepoxides;

Part 7 is concerned with the oxyalkylation of the products described inPart 6, preceding;

Part 8 is concerned with reactions involving the two preceding types ofmaterials and examples obtained by such reactions. Generally speaking,this involves nothing more than a reaction between two moles of apreviously prepared oxyalkylated amine-modified phenol-aldehyde resincondensate as described and one mole of a polyepoxide so as to yield anew and larger resin molecule or comparable product;

Part 9 is concerned with the resolution of petroleum emulsions of thewater-in-oil type by means of the previously described chemicalcompounds or reaction products; and

Part 10 is concerned with uses for the products herein described eitheras such or after modification, including any applications other thanthose involving resolution of petroleum emulsions of the water-in-oiltype.

PART 1 As will be pointed out subsequently, the preparation ofpolyepoxides may include the formation of a small amount of materialhaving more than two epoxide groups per molecule. If such compounds areformed they are perfectly suitable except to the extent they may tend toproduce ultimate reaction products which are not solventsoluble liquidsor low-melting solids. Indeed, they tend to form thermosetting resins orinsoluble materials. Thus, the specific objective by and large is toproduce diepoxides as free as possible from any monoepoxides and as freeas possible from polyepoxides in which there are more than two epoxidegroups per molecule. Thus, for practical purposes what is saidhereinafter is largely limited to polyepoxides in the form ofdiepoxides.

As has been pointed out previously one of the reactants employed is adiepoxide reactant. It is generally obtained from phenol(hydroxybenzene) or substituted phenol. The ordinary or conventionalmanufacture of the epoxides usually results in the formation of aco-generic mixture as explained subsequently. Preparation of the monomeror separation of the monomer from the remaining mass of the co-genericmixture is usually expensive. If monomers were available commercially ata low cost, or if they could be prepared without added expense forseparation, our preference would be to use the monomer. Certain monomershave been prepared and described in the literature and will be referredto subsequently. However, from a practical standpoint one must weigh theadvantage, if any, that the monomer has over other low molal polymersfrom a cost standpoint; thus, we have found that one might as wellattempt to prepare a monomer and fully recognize that there may bepresent, and probably invariably are present, other low molal polymersin comparatively small amounts. Thus, the materials which are most aptto be used for practical reasons are either monomers 6 with some smallamounts of polymers present or mixtures which have a substantial amountof polymers present. Indeed, the mixture can be prepared free frommonomers and still be satisfactory. Briefly, then our preference is touse the monomer or the monomer with the minimum amount of higherpolymers.

It has been pointed out previously that the phenolic nuclei in theepoxide reactant may be dire tly united, or united through a variety ofdivalent radicals. Actually, it is our preference to use those which arecommercially available and for most practical purposes it meansinstances where the phenolic nuclei are either united directly withoutany intervening linking radical, or else united by a ketone residue orformaldehyde residue. The commercial bis-phenols available now in theopen market illustrate one class. The diphenyl derivatives illustrate asecond class, and the materials obtained by reacting substitutedmonofunctional phenols with an aldehyde illustrate the third class. Allthe various known classes may be used but our preference rests withthese classes due to their availability and ease of preparation, andalso due to the fact that the cost is lower than in other examplcs.

Although the diepoxide reactants can be produced in more than one way,as pointed out elsewhere, our preference is to produce them by means ofthe epichlorohydrin reaction referred to in detail subsequently.

One epoxide which can be purchased in the open market and contains onlya modest amount of polymers corresponds to the derivative of bis-phenolA. It can be used as such, or the monomer can be separated by an addedstep which involves additional expense. This compound of the followingstructure is preferred as the epoxide reactant and will be used forillustration repeatedly with the full understanding that any of theother 'epoxides described are equally satisfactory, or that the higherpolymers are satisfactory, or that mixtures of the monomer and higherpolymers are satisfactory. The formula for this compound is suitableepoxide derived therefrom. Bis-phenol A is dihydroxy-diphenyl-dimethylmethane, with the 4,4 isomers predominating and with lesser quantitiesof the 2,2"

and 4,2 isomers being present. It is immaterial which one of theseisomers is used and the commercially available mixture is entirelysatisfactory.

Attention is again directed to the fact that in the instant part, towit, Part 1, and in succeeding parts, the text is concerned almostentirely with epoxides in which there is no bridging radical or thebridging radical is derived from an aldehyde or a ketone. It would beimmaterial if the divalent linking radical would -be derived from theother groups illustrated for the reason that nothing more than meresubstitution of one compound for the other would be required. Thus, whatis said hereinafter, although directed to one class or a few classes,applies with equal force and efifect to the other classes of epoxidereactants.

If sulfur-containing compounds are prepared they should be freed fromimpurities with considerable care for the reason that any time that alow-molal sulfurcontaining compound can react with epichlorohydrin theremay be formed a by-product in which the chlorine happened to beparticularly reactive and may represent a product, or a mixture ofproducts, which would be unusually toxic, even though in comparativelysmall concentration.

PART 2 The polyepoxides and particularly the diepoxides can be derivedby more than one method as, for example, the use of epichlorohydrin orglycerol dichlorohydri-n,

A number of problems are involved in attempting to produce thesematerials free from cogeneric materials of related composition. For adiscussion of these difiiculties, reference is made to U; S. Patent No.2,819,212, beginning at column 7, line 21.

pounds are described in the two patents just mentioned.

TABLEI Ex- Patent ample Diphenol Dtglyeidyl ether refernumber ence 1AOH,(C H4OH)1 Di(epoxypropoxyphenyl)methaue 2,506,486 2A CH;CH(C5H4OH).-Di(epoxypropoxyphenyl)methylmethane 2,506,486 3!. (OH:)2O(CH4OH);Di(epoxypropoxyphenyl)dimethylmethane-.. 2,506,486 4A..C,H;G(CH3)(CH4OH):.. Di(epoxypropoxyphenyl)ethylmethylmethane- 2,506,4865A.. (0:H5)]C(CflH40 )2----- Di(epoxypropoxyphenyl)diethylmethane.2,506,486 6). OHaOECsH )(CaHlOH):..Di(eopxypropoxyphenyl;methylpropylmethane 2, 506,486 7A (EH30 C H )(OH4OH)1.. Di(epoxypropoxyphenyl methylphenylmethane-.- 2,506,486 8ACzH5C(CuH5)(CeH4OH)z. Di(epoxypropoxyphenyDethylphenylmethane 2,506,4809A.. GsH1O(C5H )(O H4OH): Di(epoxypropoxyphenybgropyl hen lmethane. 2,506,486 10A. CAHQC(CH5)(CH4OH):-.. Di(epoxypropoxyphenyl) utyp enymethane" ,506,486 11A (CH Cn 4 CH s 4 z...-Di(epoxypropoxyphenyl)tolylruethane 2,506,486 12A (CHaCeH4 C(CH3)(CH OH)Di(epoxypropoxyphenyl)tolylmethylmethane 2, 506,486 13A Dihydroxydiphenyl 4,4-bis(2,3-epoxypropoxy)diphen 2, 530,353 14A(OH;)O(O4H5.GH3OH)12,2-bis(4-(2,3-ep0xypropoxy)2-tertiarybutylphenyDpropane... 2,530,353

PART 3 Subdivision B Subdivision A The preparations of the diepoxyderivatives of the diphenols, which are sometimes ethers, have beendescribed in a referred to as diglycidyl number of patents. For

As to the preparation of low-molal polymeric epoxides or mixturesreference is made to aforementioned U. S.

TABLE II I C C-C 0 Ri[R],R1OGC-C- -O R [R],.R1OCC-G H: H H: H: A H1 Hg HH;

(in which the characters have their previous significance) Example R1O-from HR10H R n 1| Remarks number B1 Hydroxy benzene CH; 1 0,1,2 Phenolknown as bis-phenol A. Low polymeric mixture about 5% or more C wheren=0, remainder largely where I =1, some where n=2. CH;

B2 do OH; 1 O, 1, 2 Phenol known as his-phenol B. See note 6 regardingB1 above.

I (IIIH: CH:

B3 Orthobutylphenol CH; 1 0,1, 2 Even though 11 is preferably 0, yet the([J usual reaction product might well eontain materials where n is l, orto a I lesser degree 2. C

B4 Orthoamylphenol OH 1 0, 1, 2 Do.

lilHl B5 Orthooctylphenol CH; 1 0, 1, 2 D0.

B6 Orthononylphenol OH; 1 0, 1, 2 Do.

(all;

137 Orthododeeylpheuol CH1 1 0,1,2 Do.

B8 Metaeresol CH: 1 0, 1,2 See prior note. This phenol used as initialmaterial is known as bis-phenol C. For other suitable bis-phenols see41H U. S. Patent 2,564,191.

TABLE II (continued) Example R O- from HR OH --R n 7!, Remarks number B9Metacresol (1H, 1 0,1,2 See priornote.

CH, 41H,

B10 Dibutyl (ortho-para) phenol. H 1 0,1,2 Do.

B11 Diamyl (ortho-pere) phenoL H 1 0 1, 2 Do.

B12 Dioctyl (ortho-para) phenol. H 1 0,1, 2 Do.

B13 Dinonyl (ortho-para) phenol. H 1 0,1,2 Do.

B14 Diamyl (ortho-para) phenol. H 1 0, 1,2 Do.

B15 do H 1 0,1,2 Do.

B16 Hydroxy benzene O ,1 0,1,2 Do.

I S-,- I 0 i B17 Diamyl phenol (orthoparaL --S-S 1 0,1,2

B18 do s- :1 0,1,2 Do.

B19 Dibutyl phenol (ortho-para), H H 1" 0,1,2 Do.

B20 do H H 1 0,1,2 Do.

B21 Dinonylphenol(ortho-para). 1% H 1 0,1,2 Do.

H H 1322,." Hydroxy benzene (I? 1 i 0, 1, 2

B23 d0 None 0 0,1,2 0-

B24 Ortho-isopropyl phenol CH; '1- 0,1,2 See priornote. As topreparation oi4,4

| isopropyhdene bis-(2-isopropylphenoll C- see U. S. Patent No.2,482,748, dated Sept. 27, 1949, to Dietzler. CH3

B25 Para-octyl phenol. '-CH -S-CH 1 0, 1, 2 See prior note. (As topreparation of the phenol sulfide see U. S. Patent No. 2,488,134, datedNov. 15, 1949. to Mikeska et a1.)

1326...... Hydroxybenzene CH3 1 0, 1, 2 See prior note. (As topreparation of the phenol sulfide see U. S. Patent No. 2,526,545.)

Subdivision C' The prior examples have been limited largely to :those inwhich there is no divalent linking radical, as in the case of diphenylcompounds, or'where the linking radical is derived from a ketone oraldehyde, particularly a ketone. Needless to say, the same procedure isemployed in converting diphenyl into a diglycidyl ether regardless ofthe nature of the bond between the two phenolic nuclei. For purpose ofillustration attention is directed to numerous other diphenols Which canbe readily converted to a suitable polyepoxide, and particularlydiepoxide, reactant.

As previously pointed out the initial phenol may be substituted, and thesubstituent group in turn may be a 11 Similar phenols which aremonofunctional, for instance, paraphenyl phenol or paracyclohexyl phenolwith an additional substituent in the ortho position, may be employed inreactions previously referred to, for instance,

with formaldehyde or sulfur chlorides to give comparable phenoliccompounds having 2 hydroxyls and suitable for subsequent reaction withepichlorohydrin, etc.

Other samples include:

on H

H R1 URI I on. H;

wherein R is a substituent selected from the class consist:

ing of secondary butyl and tertiary butyl groups and R, is a substituentselected from the class consisting of alkyl, cycloalkyl, aryl, aralkyl,and alkaryl groups, and wherein said alkyl group contains at least 3carbon atoms. See U. S. Patent No. 2,515,907.

in which the -C H groups are secondary amyl groups. 1

See U. S. Patent No. 2,504,064.

CIHII 0 13 HO OH See U. S. Patent No. 2,285,563.

(DH-CH2 See U. S. Patent No. 2,503,196.

wherein R is a member of the group consisting of alkyl, and alkoxyalkylradicals containing from 1 to 5 carbon atoms, inclusive, and aryl andchloraryl radicals of the benzene series. See U. S. Patent No.2,526,545.

R: R Qm X a Ha 12 wherein R is a substituent selected from the classconsisting of secondary butyl and tertiary butyl groups and R is asubstituent selected from the class consisting of alkyl, cycloalkyl,aryl, aralkyl, and alkaryl groups. See U. S. Patent No. 2,515,906.

OH C=CH OH See U. S. Patent No. 2,515,908.

As to sulfides, the following compound is of interest:

aldehyde or some other aldehyde, particularly compounds such as v H H OO Alkyl Alkyl Alkyl Alkyl in which R is a methylene radical, or asubstituted methylene radical which represents the residue of analdehyde and is preferably the unsubstituted methylene radical derivedfrom formaldehyde. See U. S. Patent No. 2,430,002.

See also U. S. Patent No. 2,581,919 which describes di(diaky1 cresol)sulfides which include the monosulfides, the disulfides, and thepolysulfides. The following formula represents the various dicresolsulfides of this invention:

OH CH; OH; OH

in which R and R, are alkyl groups, the sum of whose carbon atoms equals6 to about 20, and R and R, each preferably contain 3 to about 10 carbonatoms, and x is l to 4. The term sulfides" as used in this text,therefore, includes monosulfide, disulfide, and polysulfides.

PART 4 It is well known that one can readily purchase on the openmarket, or prepare, fusible, organic solvent-soluble, water-insolubleresin polymers of a composition approximated in an idealized form by theformula OH OH OH H r H1 C C O U B B. i n B In the above formula nrepresents a small whole number varying from 1 to 6, 7 or 8, or more, upto probably or 12 units, particularly when the resin is subjected toheating under a vacuum as described in the literature. A limitedsub-genus is in the instance of low molecular weight polymers Where thetotal number of phenol nuclei varies from 3 to 6, i. e., n varies from 1to 4; R represents an aliphatic hydrocarbon substituent, generally analkyl radical having from 4 to carbon atoms, such as a butyl, amyl,hexyl, decyl or dodecyl radical. Where the divalent bridge radical isshown as being derived from formaldehyde it may, of course, be derivedfrom any other reactive aldehyde having 8 carbon atoms or less.

Because a resin is organic solvent-soluble does not mean it isnecessarily soluble in any organic solvent. This is particularly truewhere the resins are derived from trifunctional phenols as previouslynoted. However, even when obtained from a difunctional phenol, forinstance, paraphenylphenol, one may obtain a resin which is not solublein a nonoxygenated solvent, such as benzene, or xylene, but requires anoxygenated solvent such as a low molal alcohol, dioxane, ordiethyleneglycol diethylether. Sometimes a mixture of the two solvents(oxygenated and nonoxygenated) Will serve. See Example 9a of U. S.Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser.

The resins herein employed as raw materials must be soluble in anonoxygenated solvent, such as benzene or xylene. This presents noproblem insofar that all that is required is to make a solubility teston commercially available resins, or else prepare resins which arexylene or benzene-soluble as described in aforementioned U. S. PatentNo. 2,499,365, or in U. S. Patent No. 2,499,368, dated March 7, 1950, toDe Groote and Keiser. In said patent there are describedoxyalkylation-susceptible, fusible, nonoxygenated-organicsolvent-soluble, water-insoluble, low-stage phenol-aldehyde resinshaving an average molecular weight corresponding to at least 3 and notover 6 phenolic nuclei per resin molecule. These resins are difunctionalonly in regard to methylol-forming reactivity, are derived by reactionbetween a difunctional monohydric phenol and an aldehyde having not over8 carbon atoms and reactive toward said phenol, and are formed in thesubstantial absence of trifuncti'onal phenols. The phenol is of theformula in which R is an aliphatic hydrocarbon radical having at least 4carbon atoms and not more than 24 carbon atoms, and substituted in the2,4,6 position.

If one selected a resin of the kind just described previously andreacted approximately one mole of the resin with two moles offormaldehyde and two moles of a basic nonhydroxylated secondary amine asspecified, following the same idealized over-simplification previouslyreferred to, the resultant product might be illustrated The basicnonhydroxylated amine may be designed thus:

RI HN In conducting reactions of this kind one does not necessarilyobtain a hundred percent yield for obvious reasons. Certain sidereactions may take place. For instance, 2 moles of amine may combinewith one mole of the aldehyde, or only one mole of the amine may combinewith the resin molecule, or even to a very slight extent, -if at all, 2resin units may combine without any amine in the reaction product, asindicated in the following formulas:

As has been pointed out previously, as far as the resin unit goes onecan use a mole of aldehyde other than formaldehyde, such asacetaldehyde, propionaldehyde or butyraldehyde. The resin unit may beexemplified thus:

OH I" OH "I OH I R,

R R 'n R in which R' is the divalent radical obtained from theparticular aldehyde employed to form the resin. For reasons which areobvious the condensation product obtained appears to be described bestin terms of the method of manufacture.

As previously stated the preparation of resins, the kind herein employedas reactants, is Well known. See previously mentioned U. S. Patent2,499,368. Resins can be made using an acid catalyst or basic catalystor a catalyst having neither acid nor basic properties in the ordinarysense or without any catalyst at all. It is preferable that the resinsemployed be substantially neutral. In other words, if prepared by usinga strong acid as a catalyst such strong acid should be neutralized.Similiarly, if a strong base is used as a catalyst 'it is preferablethat the base be neutralized although We have found that sometimes thereaction described proceeded more rapidly in the presence of a smallamount of a free base. The amount may be as small as a 200th of apercent and as much as a few l0ths of a percent. Sometimes moderateincrease in caustic soda and caustic potash may be used. However, themost desirable procedure in practically every case is to have the resinneutral.

In preparing resins one does not get a single polymer, i. e., one havingjust 3 units, or just 4 units, or just 5 units, or just 6 units, etc. Itis usually a mixture; for instance, one approimating 4 phenolic nucleiwill have some trimer and pentamer present. Thus, the molecular weightmay be such that it corresponds to a fractional value for n as, forexample, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins we found no reason for usingother than those which are lowest in price and most readily availablecommercially. For

purposes of convenience suitable resins are characterized in thefollowing table: 1

TABLE III- M01. wt. 3'' of resin ample R Position derived n moleculenumber of R iromased on n+2) 1a Tertiary bntyl Para Formal- 3 882.5

dehyde 9a Secondary butyl. Ortho.-- o 3. 882.5 30 Tertiary amyl Para d3. 959.5 411 Mixed secondary Ortho.-- .d0 3. 805.5

and tertiary amyi. r0 3. 805. 3. 1,036. 3. 1,190. 3. 1, 267 3. 1,Dodeeyl 3. 1, Tertiary butyl 3.

hyde Tertiary amyl do do 3. 1, Nonyl do d 3. 1, Tertiary hutyl--. o Butal- 3. 1,

de yde Tertiary amyl... d0 o 3. 1, Non do. do 3. I, Tertiary butyl d0Propion- 3. 1,

aldehyde Tertiary amyl d 1, Nonyl 1, Tertiary butyl Tertiary amyl.

Nonyl Tertiary amyl.

Hexyl PART 5 As has been pointed out, the amine herein employed as areactant is a basic secondary polyamine and preferably a strongly basicsecondary polyamine free from hydroxyl groups, free from primary aminogroups, free from substituted imidazoline groups, and free fromsubstituted tetrahydropyrimidine groups, in which the hydrocarbonradicals present, whether monovalent or divalent are alkyl alicyclic,arylalkyl, or heterocyclic in character.

Previous reference has been made to a number of polyamines which aresatisfactory for use as reactants in the instant condensation procedure.The cheapest amines available are polyethylene amines and polypropyleneamines. In the case of the polyethylene amines there may be as many as5, 6 or 7 nitrogen atoms. Such amines are susceptible to terminalalkylation or the equivalent, i. e., reactions which convert theterminal primary amino group or groups into a secondary or tertiaryamine radical. In the case of polyamines having at least 3 nitrogenatoms or more, both terminal groups could be converted into tertiarygroups, or one terminal group could be converted into a tertiary groupand the other into a secondary amino group. By way of example thefollowing formulas are included. It will be noted they include somepolyamines which, instead of being obtained from dichloride, propylenedichloride, or the like, are obtained from dichloroethyl ethers in whichthe divalent radical has a carbon atom chain interrupted by an oxygenatom:

CH; CHI

Another procedure for producing suitable polyamines is a reactioninvolving first an alkylene imine, such as ethylene imine or propyleneimine, followed by an alkylating agent of the kind described, forexample, dimethylsulfate, or else a reaction which involves an alkyleneoxide, such as ethylene oxide or propylene oxide, followed by the use ofan alkylating agent or the comparable procedure in which a halide isused.

What has been said previously may be illustrated by reactions involvinga secondary alkyl amine, or a secondary aralkyl amine, or a secondaryalicyclic amine, such as dibutylamine, dibenzylamine, dicyclohexylamine,or mixed amines with an imine so as to introduce a primary amino groupwhich can be reacted with an alkylating agent, such as dimethyl sulfate.In a somewhat similar procedure the secondary amine of the kind justspecified can be reacted with an alkylene oxide such as ethylene oxide,propylene oxide, or the like, and then reacted with an imine followed bythe final step noted above in order to convert the primary amino groupinto a secondary amino group.

Reactions involving the same two classes of reactants previouslydescribed, i. e., a secondary amine plus an imine plus an alkylatingagent, or a secondary amine plus an alkylene oxide plus an imine plus analkylating agent, can be applied to another class of primary amineswhich are particularly desirable for the reason that they introduce adefinite hydrophile effect by virtue of an ether linkage, or repetitiousether linkage, are certain basic polyether amines of the formula inwhich x is a small whole number having a value of 1 or more, and may beas much as 10 or 12; n is an integer having a value of 2 to 4,inclusive; m represents the numeral 1 to 2; and m represents a number 0to 1, with the proviso that the sum of m plus m equals 2; and R has itsprior significance, particularly as a hydrocarbon radical.

The preparation of such amines has been described in the literature andparticularly in two United States patents, to wit, U. S. Nos. 2,325,514,dated July 27, 1943, to Hester and 2,355,337, dated August 8, 1944, to

17 Spence. The latter patent describes typical haloalkyl ethers such asCH3002H4CI CH-OH2 CH2 H-CH2O C2H4OCzN4Br Other somewhat similarsecondary monoamines equally suitable for such conversion reactions inorder to yield appropriate secondary amines, are those of thecomposition as described in U. S. Patent No. 2,375,659, dated May 8,1945, to Jones et al. In the above formula R may be methyl, ethyl,propyl, amyl, octyl, etc.

Other suitable secondary amines which can be converted into appropriatepolyamines can be obtained from products which are sold in the openmarket, such as may be obtained by alkylation of cyclohexylmethylamineor the alkylation of similar primary amines, or for that matter, aminesof the kind described in U. S. Patent No.. 2,482,546, dated September20, 1949, to Kaszuba, provided there is no negative group or halogenattached tothe phenolic nucleus. Examples include the following: betaphenoxyethylamine, gamma phenoxypropylamine,beta-phenoxy-alpha-methylethylamine, and beta-phen oxypropylamine.

Other secondary monoamines suitable for conversion into polyamines arethe kind described in British Patent. No. 456,517 and may be illustratedby In light of the various examples of polyamines which have beenusedfor illustration it may be well to refer again to the fact thatpreviously the amine was shown as:

with the statement that such presentation is an oversimplification. Itwas pointed out that at least one oc-- 'currence of R must include asecondary amino radical of the kind specified. Actually, if thepolyamine radical contains two or more secondary amino groups theaminemay react to two different positions and thus the same amine mayyield comounds in which R and R are dis 18 similar. This is illustratedby reference to two prior examples:

CH9 CH3 H N propyleneN propyleneN In the first of the two above formulasif the reaction involves a terminal amino hydrogen obviously theradicals attached to the nitrogen atom, which in turn combines with themethylene bridge, would be different than if the reaction took place atthe intermediate secondary amino radical as differentiated from theterminal group. Again, referring to the second formula above, although aterminal amino radical is not involved it is obvious again that onecould obtain two different structures for the radicals attached to thenitrogen atom united to the methylene bridge, depending whether thereaction took place at either one of the two outer secondary aminogroups, or at the central secondary amino group. If there are two pointsof reactivity towards formaldehyde as illustrated by the above examplesit is obvious that one might get a mixture in which in part the reactiontook place at one point and in part at another point. Indeed, there arewell known suitable polyamine reactions where a large variety ofcompounds might be obtained due to such multiplicity of reactiveradicals. This can be illustrated by the following formula:

CH; CH:

Over and above the specific examples which have appeared previously,attention is directed to the fact that added suitable polyamines areshown in subsequent Table II.

PART 6 The products obtained by the herein described proc essesrepresent cogeneric mixtures which are the result of a condensationreaction or reactions. Since the resin molecule cannot be definedsatisfactorily by formula, although it may be so illustrated in anidealized simplification, it is difficult to actually depict the finalproduct of the cogeneric mixture except in terms of the process itself.

Previous reference has been made to the fact that the procedure hereinemployed is comparable, in a general way, to that which corresponds tosomewhat similar derivatives made either from phenols as differentiatedfrom a resin, or in the manufacture of a phenol-aminealdehyde resin; orelse from a particularly selected resin and an amine and formaldehyde inthe manner described in Bruson Patent No. 2,031,557 in order to obtain aheat-reactive resin. Since the condensation products obtained are notheat-convertible and since manufacture is not restricted to a singlephase system, and since temperatures up to C. or thereabouts may beemployed, it is obvious that the procedure becomes comparatively simple.Indeed, perhaps no description is necessary over and above what has beensaid previously, in light of subsequent examples. However, for purposeof clarity the following details are included.

A convenient piece of equipment for preparation of these cogenericmixtures is a resin pot of the kind described in aforementioned U. S.Patent No. 2,499,368. In most instances the resin selected is not apt tobe a fusible liquid at the early or low temperature stage of reaction ifemployed as subsequently described; in fact, usually it is apt to be asolid at distinctly higher temperatures, for instance, ordinary roomtemperature. Thus, we have found it convenient to use a solvent andparticularly one which can be removed readily at a corn parativelymoderate temperature, for instance, at 150i C. A suitable solvent isusually benzene, xylene, or a comparable petroleum hydrocarbon or amixture of such or similar solvents. Indeed, resins which are notsoluble except in oxygenated solvents or mixtures containing suchsolvents are not here included asraw materials. The reaction can beconducted in suchaway that the initial reaction, and perhaps the bulk ofthe reaction, takes place in a polyphase system. However, if desirable,one can use an oxygenated solvent such as a lowboiling alcohol,including ethyl alcohol, methyl alcohol, etc. Higher alcohols can beused or one can use a com paratively non-volatile solvent such asdioxane of the diethylether of ethylene glycol. One can also use mixtureof benzene or xylene and such oxygenated solvents. Note that the use ofsuch oxygenated solvent is not required in the sense that it is notnecessary to use an initial resin which is soluble only in an oxygenatedsolvent as just noted, and it is not necessary to have a single phasesystem for reaction.

Actually, water is apt to be present as a solvent for the reason that inmost cases aqueous formaldehyde is employed, which may be the commercialproduct which is approximately 37%, or it may be diluted down to about30% formaldehyde. However, pa'raformaldehyde can be used but it is morediflicult perhaps to add a solid material instead of the liquidsolution, and, everything else being equal, the latter is apt to be moreeconomical. In any event, Water'is present as water of reaction. If thesolvent is completely removed at the end of the process, no problem isinvolved if, the material is used for any subsequent reaction. However,if the reaction mass is going to be subjected to some further reactionwhere the solvent may be objectionable, as in the case of ethyl or hexylalcohol, and if there is to be subsequent oxy'alkylation, then,obviously, the alcohol should not be used or else it should be removed.The fact that an oxygenated solvent need not be, em ployed, of course,is an advantage for reasons stated.

The products obtained, depending on the reactants selected, may bewater-insoluble or water-dispersible, or water-soluble, or close tobeing water-soluble. Water solubility is enhanced, of course, by makinga solution in the acidified vehicles such as a dilute solution, forinstance, a 5% solution of hydrochloric acid, acetic acid, hydroxyaceticacid, etc. One also may convert the finished product into salts bysimply adding a stoichiometric amount of any selected acid and removingany water present by refluxing with benzene'or the like. In fact, theselection of the solvent employed may depend in part whether or not theproduct at the completion of the reaction is to be converted into a saltform.

We have found no particular advantage in using a low temperaturein theearly stage of the reaction because, and for reasons explained, this isnot necessary, although it does apply in some other procedures that, ina general way, bear some similarity to the present procedure. There isno objection, of course, tov giving the reaction an opportunity'toproceed as far as it will at some low temperature, for instance, 30 to40 but ultimately one must employ the higher temperature in order toobtain products of the kind herein described. If a:lower temperaturereaction is used initially the period is not critical, in fact, it maybe anything from a fewhoursup-to-24 hours. We have not found any casewhere it was-necessary or even desirable to hold the low temperaturestage for more than 24 hours. In fact, we arenot-convinced there is anyadvantage in holding it.at :this:stage for more than 3 to 4 hours at themost. This, again, is a matter of convenience largely for one reason.Inheating and stirring the reaction mass thereis a:tendency forformaldehyde to belost. Thus, if the reaction can be conducted at alower temperature so as to use up part of the formaldehyde at such lowertemperature,

20 then the amount of unreacted formaldehyde is decreased subsequentlyand makes it easier to prevent any loss. Here, again, this lowertemperature is not necessary by virtue of heat convertibility aspreviously referred to.

If solvents and reactants are selected so the reactants and products ofreaction are mutually soluble, then agitation is required only to theextent that it helps cooling or helps distribution of the incomingformaldehyde. This mutual solubility is not necessary as previouslypointed out but may be convenient under certain circumstances. On theother hand, if the products are not mutually soluble then agitationshould be more vigorous for the reason that reaction probably takesplace principally at the interfaces and the more vigorous the agitationthe more interfacial area. The general procedure employed is invariablythe same when adding the resin and the selected solvent, such as benzeneor xylene. Refiuxing should belong enough to insure that the resinadded, preferably in a powdered form, is completely dissolved. However,if the resin is prepared as such it may be added in solution form, justas preparation is described in aforementioned U. S. Patent 2,499,368.After the resin is in complete solution the polyamine is added andstirred. Depending on the polyamine selected, it may or may not besoluble in the resin solution. If it is not soluble in the resinsolution it may be soluble in the aqueous formaldehyde solution. If so,the resin then will dissolve in the formaldehyde solution as added, andif not, it is even possible that the initial reaction mass could be athree-phase system instead of a two-phase system although this would beextremely unusual. This solution, or mechanical mixture, if notcompletely soluble is cooled to at least the reaction temperature orsomewhat below, for example 35 C. or slightly lower, provided thisinitial low temperature stage is employed. The formaldehyde is thenadded in a suitable form. For reasons pointed out we prefer to use asolution and whether to use a commercial 37% concentration is simply amatter of choice. In large scale manufacturing there may be someadvantage in using a 30% solution of formaldehyde but apparently this isnot true on a small laboratory scale or pilot plant scale. 30%formaldehyde may tend to decrease any formaldehyde loss or make iteasier to control unrcactcd formaldehyde loss.

On a large scale if there is any difficulty with formaldehyde .losscontrol, one can use a more dilute form of formaldehyde, for instance, a30% solution. The reaction can be conducted in an autoclave and noattempt made to remove water until the reaction is over. Generallyspeaking, such a procedure is much less satisfactory for a number ofreasons. For example, the reaction does not seem to go to completion,foaming takes place, and other mechanical or chemical difficulties areinvolved. We have found no advantage in using solid formaldehyde becauseeven here water of reaction is formed.

Returning again to the preferred method of reaction and particularlyfrom the standpoint of laboratory procedure employing a glass resin pot,when the reaction has proceeded as one can reasonably expect at a lowtemperature, for instance, after holding the reaction mass with orwithout stirring, depending on whether or not it is homogeneous, at 30or 40 C. for 4 or 5 hours, or at the most, up to 10-24 hours, we thencomplete the reaction by raising the temperature up to C., orthereabouts as required. The initial low temperature procedure can beeliminated or reduced to -merely the shortest period of time which.avoids loss of polyamine or formaldehyde. At a higher temperature weuse a phase-separating trap and subject the mixture to refluxcondensation until the water of reaction and the water of solution ofthe formaldehyde is eliminated. We then permit the temperature to riseto :some- 21 where about 100 C., and generally slightly above 100 C. andbelow 150 C. by eliminating thesolvent or part of the solvent so thereaction mass stays within this predetermined range. This period ofheating and re- 22 xylene, i. e., 600 grams. The mixture was refluxeduntil solution was complete. Itwas then adjusted to approximately 30 to35 C. and 176 grams of symmetrical dimethylethylene diamine added. Themixture was fluxing, after the water is eliminated, is continued untilstirred vigorously and formaldehyde added slowly. In the reaction massis homogeneous and then for one to this particular instance theformaldehyde used was a 30% three hours longer. The removalof thesolvents is consolution and 200 grams were employed which were ducted ina conventional manner in the same way as the added in a little short of3 hours. The mixture was removal of solvents in resin manufactured asdescribed stirred vigorously and kept within a temperature range inaforementioned U. S. Patent No. 2,499,368. of 30 to 46 C. for about 19hours. ,At the end of Needless to say, as far as the ratio of reactantsgoes this time it was refluxed, using a phase-separating trap we haveinvariably employed approximately one mole and a small amount of aqueousdistillate withdrawn from of the resin based on the molecular weight ofthe resin time to time. The presence of unreacted formaldehyde molecule,2 moles of the secondary polyamine and 2 was noted. Any unreactedformaldehyde seemed to dismoles of formaldehyde. In some instances wehave appear within approximately two to three hours after added a traceof caustic as an added catalyst but have refluxing started. As soon asthe odor of formaldehyde found no particular advantage in this. In othercases was no longer detectible the phase-separating trap was we haveused a slight excess of formaldehyde and, set so as to eliminate all thewater of solution and reagain, have not found any particular advantagein this. action. After the water was eliminated part of the In othercases we have used a slight excess of amine xylene was removed until thetemperature reached apand, again, have not found any particularadvantagein proximately 152 C., or slightly higher. The mass was sodoing. Whenever feasible we have checked the comkept at this highertemperature for three to four hours pleteness of reaction in the usualways, including the and reaction stopped. During this time, anyadditional amount of water of reaction, molecular weight, and waterwhich was probably water of reaction which had particularly in someinstances have checked whether or formed, was eliminated by means of thetrap. The not the end-produce showed surface-activity, particuresidualxylene was permitted to stay in the cogeneric larly in adilute aceticacid solution. The nitrogen content mixture. A small amount of thesample was heated after removal of unreacted polyamine, if any ispresent, on a water bath to remove the excess xylene and the is anotherindex. residual material was dark red in color and had the In light ofwhat has been said previously, little more consistency of a sticky fluidor tacky resin. The overall need be said as to the actual procedureemployed for time for reaction was somewhat less than 30 hours. In thepreparation of the herein described condensation other examples, itvaried from a little over 20 hours up products. The following examplewill serve by way of to 36 hours. The time can be reduced by cutting theillustration: low temperature period to approximately 3 to 6 hours.Example 11, Note that in Table IV following there are a large number ofadded examples illustrating the same proce- The p -a y resm s t n thathas b dure. In each case the initial mixture was stirred and ldentlfiedprevlously as Example It Was Obtalned held at a fairly low temperature(30 to C.) for a from a para-tertiary butylphenoh and formaldehydeperiodof several hours. Then refluxing was employed The resin was preparedusing an acid catalyst which was 40 til th odor of formaldehydedisappeared. After the Completely l z d at the end of the reactlon. Theodor of formaldehyde disappeared the phase-separating molecular weightof the resin was 882.5. This corrfitrap was employed to separate out allthe water, both sponded to an av rag of a t 3 /2 ph l a the solution andcondensation. After all the water had the Value for n whi h xclud s the2 xternal 111161 been separated enough xylene was taken out to have theo the r6511! was y a ImXwre havlllg 3 11110161 final product reflux forseveral hours somewhere in the and 4 nuclei, excluding the 2 externalnuclei, or 5 and e of 145 to 150 C., or thereabouts. Usually the 6overall nuclei. The resin so obtain d In a neutr l mixture yielded aclear solution by the time the bulk of state had a light amber color.the water, or all of the water, had been removed.

882 grams of the resin identified as 1a preceding were Note that aspointed out previously, this procedure is powered and mixed with asomewhat lesser weight of illustrated by 24 examples in Table IV.

TABLE IV Strength of Reac- Reac- Max. Ex. Resin Amt., Amine used andamount formalde- Solvent used. tlon tion distill. No, u ed grg, hydesoln. and amt. temp., time, temp.,

and amt. 0. hrs, 0.

1b. 1a..-.- 882 AmineA,176grarns 30%,200 g... Xylene 600 g. 20-23 26 152Amine A, 88 grams 30%, 100 g... Xylene 450 g 20-21 24 150 Amine A, 88grams-.. 30%,100g Xylene 550 g 20-22 28 151 37%, Big... Xylene400 20-2836 144 37%, 81 g Xylene 450 g 22-30 25 156 37%,81 g.- Xylene e00 21-2832 150 200 30 145 37%, g-.. 35 14s 7%, tn.- 35 143 37%, 81 g. 31 14537%,81 Xylene 500 m- 21-26 24 146 37%, 81 g. Xylene 550 g 22-25 36 15137%, 81 g Xylene 400 15.... 25-38 32 37%,31 Xylene400 g 21-24 30 15237%, 81 g Xylene 550 g.. 21-26 27 145 20-23 25 141 22-27 29 143 23-25 36149 21-26 32 14s 30 ,,,10o Xylene 500 m. 21-23 30 148 30%, 100 g...Xylene 500 g 20-26 36 152 3 100 g... Xylene 440 g 21-24 32 150 37%,81g.Xylene 500 g 2l28 25 150 24b 2511.... 391 Amine 11,141 grams 30%, 50 gXylene 350 g.. 21-22 28 151 As to the formulas oi? theabove aminesreferred to as; amine A through amine H, inclusive, see immediatelybelow:

at n Amine A.- \NQIHANZ CHs" A n B- H Amine 0- NonnN CHI-'- HI PART 7 Inpreparing oxyalkylated derivatives of products of the kind which appearas examples in Part 3, we have found it particularly advantageous to uselaboratory equipment which permits continuous oxypropylation andoxyethylation. The oxyethylation step is, of course, the same as theoxypropylation step insofar that two low boiling liquids are handled ineach instance. The oxyalkylation step is carried out in a manner whichis substantially conventional for the oxyalkylation of comr poundshaving labile hydrogen atoms, and for that reason a detailed descriptionof the procedure is omitted and the process will simply be illustratedby the following examples:

Example 10 The oxyalkylation-susceptible compound employed is the onepreviously described and designated as Example lb. Condensate 1b was inturn obtained from symmetrical dimethylethylene diamine and the resinpreviously identified as Example 1a. Reference to Table III shows thatthis particular resin is obtained from paratertiarybutylphenol andformaldehyde. 10.82 pounds of this resin condensate were dissolved in 6pounds of solvent (xylene) along with one pound of finely powderedcaustic soda as a catalyst. Adjustment was made in the autoclave tooperate at a temperature of approximately 125 C. to 130 C., and at apressure of about to or pounds, 25 pounds at the most. In somesubsequent examples pressures up to pounds were employed.

The time regulator was set so as to inject the ethylene oxide inapproximately three-quarters of an hour and then continue stirring for15 minutes or longer, a total f added catalyst and no added solvent.

ime f one hour. The reaction went readily and, as a matter of fact, thoxide was taken up almost immediately. Indeed the reaction was completein less than an hour. The speed of reaction, particularly at e low pressre, undoubtedly was due-in a large measureto excellent agitation andalso to the comparatively high concentration of catalyst.v The amount ofethylene oxide introduced was equal in weight to the initialcondensation product, to wit, 10.82 pounds. This represented a molalratio of 2.4.6' moles of ethylene oxide per mole of condensate.

The theoretical molecular weight at the end of the reaction period was2.164,. A comparatively small sample, less than 50 grams, was withdrawnmerely for examination as far as; solubility or emulsifying power was.concerned and also for the purpose of making some tests on various oilfield emulsions. The amount withdrawn was so small that no cognizance ofthis fact is included in the data, or subsequent data, or in the datapresented in tabular form in subsequent Tables V and The size of theautoclave employed was 25 gallons. In innumerable comparableoxyalkyl'ations we have withdrawn a substantial portion at the end ofeach step and. continued oxyalkylation on a partial residual sample.This was not the case in this particular series. Certain examples wereduplicated as hereinafter noted and subjected to oxyalkylation with adifferent oxide.

This examplev simply illustrates the further oxyalkyb ation of Example1c, preceding. As previouslystated', the oxyalkylation-susceptiblecompound, to wit, Example 1b, present at the beginning of the stage wasobviously the same as at the end of the prior stage (Example 1c), towit, 10.82 pounds. The amount of'oxide present in the initial step was10.82 pounds, and the amount of solvent remained the same. The amount ofoxide added was another 10.82 pounds, all addition of oxide in thesevarious stages being based on the addition of this particular amount.Thus, at the end of the oxyethylation step the amount of oxide added wasa total of 21.64 pounds and the molal ratio of ethylene oxide to resincondensate was 49.2 to l. The theoretical molecular weight was 3246.

The maximum temperature during the operation was to C. The maximumpressure was in. the range of 15 to 25 pounds. The time period was oneand three-quarter hours.

Example 30 The oxyalkylation proceeded in the same manner described inExamples 10 and 2c. There was no added solvent and no added catalyst.The oxide added was 10.82 pounds and the total oxide at the end of theoxyethylation step was 32.46 pounds. The molal ratio of oxide tocondensate was 73.8 to 1. Conditions as far as temperature and pressureand time were concerned were all the same as in Examples 1c and 2c. Thetime period was somewhat longer than in previous examples, to wit, 2hours.

Example 4c The oxyethylation was continued and the amount of oxide addedagain was 10.82 pounds. There was no The theoretical molecular weight atthe end of the reaction period was 5410. The molal ratio of oxide tocondensate was 98.4 to 1. Conditions as. far as. temperature andpressure were Concerned were the same as in previous examples. The timeperiod was slightly longer, to wit, 2 /2 hours. The reactionunquestionably began to slow up somewhat.

Example 50 The oxyethylation continued with the introduction of another10.82 pounds of ethylene oxide. No more solvent was introduced but .3pound caustic soda was added. The theoretical molecular weight at theend of the agitation period was 6492, and the molal ratio of oxide toresin condensate was 123 to 1. The time period, however, dropped to 2hours. Operating temperature and pressure remained the same as in theprevious example.

Example 60 The same procedure was followed as in the previous examples.The amount of oxide added was another 10.82 pounds, bringing the totaloxide introduced to 64.92 pounds. The temperature and pressure duringthis period were the same as before. There was no added solvent. Thetime period was 3 hours.

Example 70 The same procedure was followed as in the previous sixexamples without the addition of more caustic or more solvent. The totalamount of oxide introduced at the end of the period was 75.74 pounds.The theoretical molecular weight at the end of the oxyalkylation periodwas 8656. The time required for the oxyethylation was a bit longer thanin the previous step, to wit, 4 hours.

Example 8c This was the final oxyethylation in this particular series.There was no added solvent and no added catalyst. The total amount ofoxide added at the end of this step was 86.56 pounds. The theoreticalmolecular weight was 9738. The molal ratio of oxide to resin condensatewas 196.8 to one. Conditions as far as temperature and pressure wereconcerned were the same as in the previous examples and the timerequired for oxyethylation was 5 hours.

The same procedure as described in the previous examples was employed inconnection with a number of the other condensates described previously.All these data have been presented in tabular form in a series of fourtables, Tables V and VI, VII and VIII.

In substantially every case a 25-gallon autoclave was employed, althoughin some instances the initial oxyethylation was started in a 15-gallonautoclave and then transferred to a 25-gallon autoclave. This isimmaterial but happened to be a matter of convenience only. The solventused in all cases was xylene. The catalyst used was finely powderedcaustic soda.

Referring now to Tables V and VI, it will be noted that compoundsthrough 40c were obtained by the use of ethylene oxide, whereas 410through 800 were obtained by the use of propylene oxide alone.

Thus, in reference to Table V it is to be noted as follows:

The example number of each compound is indicated in the first column.

The identity of the oxyalkylation-susceptible compound, to wit, theresin condensate, is indicated in the second column.

The amount of condensate is shown in the third column.

Assuming that ethylene oxide alone is employed, as happens to be thecase in Examples 10 through 40c, the

26 amount of oxide present in the oxyalkylation derivative is shown incolumn 4, although in the initial step since no oxide is present thereis blank.

When ethylene oxide is used exclusively the 5th column is blank.

The 6th column shows the amount of powdered caustic soda used as acatalyst, and the 7th column shows the amount of solvent employed.

The 15th column shows the theoretical molecular weight at the end of theoxyalkylation period.

The 8th column states the amount of condensate present in the reactionmass at the end of the period.

As pointed out previously, in this particular series the amount ofreaction mass withdrawn for examination was so small that it was ignoredand for this reason the resin condensate in column 8 coincides with thefigure in column 3.

Column 9 shows the amount of ethylene oxide employed in the reactionmass at the end of the particular period.

Column 10 can be ignored insofar that no propylene oxide was employed.

Column 11 shows the catalyst at the end of the reaction period.

Column 12 shows the amount of solvent at the end of the reaction period.

Column 13 shows the molal ratio of ethylene oxide to condensate.

Column 14 can be ignored for the reason that no propylene oxide wasemployed.

Referring now to Table VIII. the first column refers to Examples 10, 2c,30, etc.

The second column gives the maximum temperature employed during theoxyalkylation step and the third column gives the maximum pressure.

The fourth column gives the time period employed.

The last three columns show solubility tests by shaking a small amountof the compound, including the solvent present, with several volumes ofwater, xylene and kerosene. It sometimes happens that although xylene incomparatively small amounts will dissolve in the concentrated material,when the concentrated material in turn is diluted with xylene separationtakes place.

Referring to Table VI, Examples 410 through c are the counterparts ofExamples 10 through 40c, except that the oxide employed is propyleneoxide instead of ethylene oxide. Therefore, as explained previously,four columns are blank, to wit, columns 4 and 9.

Reference is now made to Table VII. It is to be noted these compoundsare designated by d numbers, 1d, 2d, 3d, etc., through and including32a. They are derived, in turn, from compounds in the c series forexample, 360, 40c, 54c and 700. These compounds involve the use of bothethylene oxide and propylene oxide. Since compounds lc through 400 wereobtained by the use of ethylene oxide, it is obvious that those obtainedfrom 360 and 400, involve the use of ethylene oxide first, and propyleneoxide afterward. inversely, those compounds obtained from 540 and 700obviously come from a prior series in which propylene oxide was usedfirst.

In the preparation of this series indicated by the small letter d, as1d, 2d, 3d, etc., the initial 0 series such as 36c, 40c, 54c, and 70c,were duplicated and the oxyalkylation stopped at the point designatedinstead of being carried further as may have been the case in theoriginal oxyalkylation step. The oxyalkylation proceeded by using thesecond oxide as indicated by the previous explanation, to wit, propyleneoxide in 1d through 16d, and ethylene oxide in 17d through 32d,inclusive.

In examining the table beginning with 1d, it will be noted that theinitial product, i. e., 360, consisted of the reaction product involving10.82 pounds of the resin It is to be noted that The Melee. wt. basedoretical value immmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmm The reason x1 eon thealkyi cmpd.

Molal ratio Ethyl. Pro 1.

oxide to oxyto ox alkyl.

cmpd.

susoept n rapt S01. vent, lbs.

Catalyst, lbs.

one could start with ethylene oxide Composition at end Oxyalkylationgenerally tends to yield lighter oxide,

Needless to say,

'The colors of the products usually vary from a reddish Such productscan be decolorized by the use of Generally speaking, the amount ofalkaline catalyst o-s' Ethl. Pro 1. cmpd., lbs.

and then use propylene oxide, and then go back to ethylene oxide; or,inversely, start with propylene oxide, then use ethylene oxide, and thengo back to propylene oxide is used along with either one of the twooxides just mentioned, or a combination of both of them.

amber tint to a definitely red, and amber.

resins initially and the resins themselves may be yellow, amber, or evendark amber. Condensation of a nitrogenous product invariably yields adarker product than the original resin and usually has a reddish color.The

but one may use a darker colored aromatic petroleum solvent.

colored products and the more oxide employed the lighter the color ofthe product. Products can be prepared in tint.

clays, bleaching chars, etc. As far as use in demulsification isconcerned, or some other industrial uses, there is no justification forthe cost of bleaching the product.

present is comparatively small and it need not be removed. Since theproducts per se are alkaline due to the presence of a basic nitrogen,the removal of the alkaline catalyst is somewhat more diilicult thanordinarily.

acid, for example, to neutralize the alkalinity one may partiallyneutralize the basic nitrogen radical also. preferred procedure is toignore the presence of the alkali unless it'is objectionable or else adda stoichiometric' caustic soda present.

tLABLE V 30 is the case for the reason that if one adds hydrochloric 35amount of concentrated hydrochloric acid equal to the solvent,

the

lbs.

0oOo33330o003333000033330000333300003333 If desired 25 Propl. Catalbs.

Oomposltion before Ethl. oxide, oxide, lyst,

d 0 .D 00000000111111112222222244444 4.400000 Q0 oml11111111111111111111111111111 1111111111 0 sm u n u m m m m m m mbbbbbbbb 0 mg iiiiamamsww u u n N n n n N n n n n n o N "IIIIIIIunnflunuuuunnuflfi s a Cc CC 5. .2 a izaianawmnmmnm condensate, 16.23pounds of ethylene oxide, 1.0 pound of caustic soda, and 6.0 pounds ofthe solvent.

It is to be noted that reference to the catalyst in Table VII refers tothe total amount of catalyst, i. e., catalyst present from the firstoxyalkylation step plus 5 oxide; or, one could use a combination inwhich butylene added catalyst, if any. The same is true in regard to thesolvent. Reference to the solvent refers to the total solvent present,i. e., that from the first oxyalkylation step plus added solvent, ifany.

In this series, it will be noted that the theoretical 10 is primarilythat no efiort is made to obtain colorless molecular weights are givenprior to the oxalkylation step and after the oxyalkylation step,although the value at the end of one step is the value at the beginningof the next step, except obviously at the very start the value dependson the theoretical molecular weight at the end sol ent employed, ifxylene, adds nothing to the color of the initial oxyalkylation step; i.e., oxyethylation for 1d through 16d, and oxypropylation for 17d through32d. It will be noted also that under the molal ratio the values of bothoxides to the resin condensate are included.

The data given in regard to the operating conditions 20 which the finalC010! is a lighter amber With a feddiSh isqsfirbstantially the same asbefore and appears in Table The products resulting from these proceduresmay contain modest amounts, or have small amounts, of the solvents asindicated by the figures in the tables. the solvent may be removed bydistillation, and particularly vacuum distillation. Such distillationalso may remove traces or small amounts of uncombined oxide, if presentand volatile under the conditions employed.

Obviously, in the use of ethylene oxide and propylene oxide incombination one need not first use one oxide and then the other, but onecan mix the two oxides and thus obtain what may be termed an indifierentoxyalkylation, i. e., no attempt to selectively add one and then theother, or any other variant.

Oxyalkylatton-suseeptible TABLE VIII Mu. Max. Solubility 1!. tom m,Time;

Water: Xylene Kerosane 1c 1:15-1:40 15-25" 1 mmmma wugnpcauheaqp do.do......

TABLE VIII-Continued Solubility Time, hrs.

Kerosene Soluble. Do.

Disperlsble.

Insoluble,

PART 8 scribed and, thus, there may or may not be suificient catalystpresent for the reaction with the diepoxide. Reference to the catalystpresent includes the residual catalyst remaining from the oxyalkylationstep in which the monoepoxide was used.

Briefly stated then, employing polyepoxides in com-- bination with anonbasic reactant the usual catalysts include alkaline materials, suchas caustic soda, caustic, potash, sodium methylate, etc. Other catalystsmay be. acidic in nature. and are of the. kind illustrated by iron andtin chloride. Furthermore, insoluble catalysts such as clay or speciallyprepared mineral catalysts have been used. If for any reason thereaction does not proceed. rapidly enough with the diglycidyl ether orother analogous reactant then a small amount of finely divided causticsoda or sodium methylate can be employed as a catalyst. The amountgenerally employed would be 1% or 2%.

It goes without saying that the reaction can take place in an inertsolvent, i. e., one that is not oxyalkylationsusceptible. Generallyspeaking, this is not conveniently an aromatic solvent such as xylene ora higher boiling coal tar solvent, or. else a. similar high boilingaromatic solvent obtained from petroleum. One, can employ an oxygenatedsolvent such as the diethylether of ethyleneglycol, or the diethyletherof propyleneglycol, or similar ethers, either alone or in combinationwith a hydrocarbon solvent. The selection of the solvent depends in parton the subsequent use of the derivatives or reaction products. If thereaction products are to be rendered solvent-free and it is necessarythat the solvent be readily removed as, for example, by the use ofvacuum distillation, then xylene or an aromatic petroleum solvent willserve. If the product is going to be subjected to oxyalkylationsubsequently, then the solvent should be. one which is notoxyalkylation-susceptible. It is easy enough to select a suitablesolvent if required in any instance but, everything else being equal,the solvent chosen should be the most economical one.

Example I'e The product was obtained by reaction between the diepoxide.previously described as diepoxide 3A and oxyalkylated resin condensate2c. Oxyalkylated condensate 2d has been described in previous Part 7'and was obtained by the oxyethylation of condensate 1b. The preparationof condensate lb was described in Part 6,

preceding. Details have been included in regard to both steps.Condensate lb, in turn, was obtained from symmetrical dimethyl, ethylenediamine (amine A); the resin employed was diethanolamine and resin 2a.;resin 2a, which, in turn, was obtained from para-tertiarybutylphenol andformaldehyde.

In any event, 325 grams of the. oxyalkylated resin condensate previouslyidentified as- 20 were dissolved in approximately an equal weight ofxylene About 3 grams of sodium methylate were added as a catalyst so.the total amount of catalyst present, including residual catalyst fromthe prior oxyalkylation, was about 3.4, grams. 1? grams of diepoxide 3Awere mixed with an. equal weight of xylene. The initial addition of thediepoxide solution was made after raising the temperature of thereaction mass to about 107 C. The diepoxide was added slowly over aperiod of about an hour. During this time the temperature was allowed toreflux at.

about 134 C. usinga phase-separating trap. A small amount of xylene wasremoved by means of the phaseseparating trap so the refluxingtemperature rose gradually to about C. The mixture was refluxed at thistemperature for about 5 hours. At the end' of this period the xylenewhich had been removed by means of the phase-separating trap wasreturned to. the mixture. A small amount of material was withdrawn andthe xylene evaporated on a hotplate in order to examine the physicalproperties. The material was an amber, or light reddish amber, viscousliquid. It was insoluble in; water; it was insoluble in gluconic acid,but it was soluble in xylene and particularly in a mixture of 8.0%xylene and 20% methanol. However, if the material. was dissolved in anoxygenated solvent and then shaken with 5%.

gluconic acid it showed a defiinite tendency to disperse,

suspend, or form a sol, and particularly in, ax'ylenemethanol mixedsolvent aspreviouslydescribed, wit-her Without the further addition of alittle. acetone.

Generally speaking, the solubility of these. derivatives is in line withexpectations by merely examining the solubility of the precedingintermediates, to wit; the oxyalkylated resin condensates prior totreatment with the diepoxide. These materials, of course, vary fromextremely water-soluble products due tosubstantial oxyethylation, tothose which conversely are water-insoluble but xylene-soluble or evenkerosene-soluble due to'high.

methylglycide as oxyalkylating agents. See, for example,

Part 1 of U. s. Patent. No. 2,692, 62. dated. July 1.1952, to De Groote.

I '25 Various examples obtained in substantially the same manner areenumerated in the following tables:

TABLE IX or their equivalent. w Dilute theresin or the diepoxide, orboth, with an inert solvent, such as xylene or the like. in

Ex. Oxy- Amt, Diop- Amt, Catalyst Xy- Molar Time of Max. No. resineongrs. oxide grs. (N 4100113), leue, ratio reaction, temp, Color andphysical state densate used grs. grs. hrs. C.

3A 17 3. 4 342 2:1 4 150 Reddish amber resinous mass 3A 8. 2. 8 280 2: 14 155 D0. 34 17 2.5 255 2:1 4 158 D0. 3A 8. 5 3.1 310 2:1 4 150 D0. 348.5 4.5 445 2:1 5 152 D0. 3A 17 3.4 342 2:1 5 155 Do. 3A 8.5 3.9 388 2:15 155 Do. 3.4 17 2.6 255 2:1 4 150 Do. 34 8. 5 4. 3 430 2:1 5 148 Do.314 8.5 3. 7 373 2:1 5 154 Do. 3A 17 4. 0 305 2:1 5 152 Do. 314 8. 5 2.5 252 2: 1 5 154 D0. 3!. 8. 5 4. 4 437 2:1 5 150 Do. 3A 8. 5 4. 2 4152:1 5 150 Do. 3.4 1.7 1.8 182 2:1 4 150 Do.

TABLE X Dlep- Amt., Catalyst Xy- Molar Time of Max. oxide grs. (NaOCHa),lene, ratio reaction, temp., Color and physical state used grs. grs.hrs. '0.

B1 27.5 3. 5 353 2:1 4 140 Reddish amber resinous mass B1 13. 8 2. 9 2352:1 3. 5 142 Do. B1 27. 5 2. 7 255 2:1 3. 5 140 Do. B1 13.8 3.2 315 2:13.5 145 D0. B1 13.8 4. 5 451 2:1 4 145 Do. B1 27. 5 3. 5 353 2:1 4 147D0. B1 13.8 3.9 303 2:1 4 140 D0. B1 27.5 2. 7 255 2: 1 4 145 D0. B1 13.8 4. 4 435 2:1 4 145 Do. B1 13.8 3.8 378 2:1 4 150 Do. B1 27.5 4.1 4072:1 4 148 Do. B1 13. 8 2. 5 257 2:1 3. 5 140 D0. B1 13.8 4. 4 442 2:1 3.5 140 Do. B1 13. 8 4. 2 420 2:1 3. 5 145 Do. B1 2. 8 1. 8 183 2:1 3. 5145 D0.

TABLE XI can be avoided by any one of the following procedures someinstances an oxygenated solvent, such as the di- Pnm mol. ethylether ofethyleneglycol may be employed. Another ELNO. 0 31 115 171 we ht ofAlgoutntof Amlounttvf procedure which is helpful is to reduce the amountof if g g ifii fgi pm He so Wm catalyst used, or reduce the temperatureof reaction by adding a small amount of initially lower boiling solvent,3,415 1, 708 such as benzene, or use benzene entirely. Also, we have 3i: found it desirable at times to use slightly less than ap- 21475 11238parently the theoretical amount of diepoxide, for in- 3:562 1,731stance, 90% to 95% instead of 100%. The reason for 3,415 1,708 3,0981,549 th1s fact may res1de 1n the possibility that the molecular 5:33weight dimensions on either the resin molecule or the 2:980 1:490diepoxide molecule actually may vary from the true 2 333 2;? molecularweight by several percent. 31490 1; 745 The condensate can be depictedin a simplified form 2% 3?! which, for convenience, may be shown thus:

(Amine) CH Resin) CH Amine) If such product is subjected tooxyalkylation reaction in- Prob m 01 volves the phenolic hydroxyls ofthe resin structure and, Ex. No. Oxyalkyl. weight of Amount of Amount ofthus, can be depicted in the following manner:

resin conreaction product, grs. solvent densate product (Am1ne)CH(Oxylkylated Resin) CH (Am1ne) 7 040 3 520 1 760 Following suchsimplification the reaction with a 111370 2: 274 1: 137 polyepoxide, andparticularly a diepoxide, would be de- 5,300 2,550 1, 325 12,590 2,5181, 259 plcted thus 18, 020 3, 604 1, 802 (AminewflfloxyalkylatedBesin)CH1(Amine) 5,300 2,550 1,325 D.G.E. 17, 410 3, 482 1, 741 15,1103, 022 1, 511

8, 120 4, 060 2, 030 (Amine)CH1(0xyalkylated Resin) CHKAmine) 10, 070 2,014 1, 007 17,550 3,532 1,755 in which D. G. E. represents a diglycldylether as speci- 15, 780 3, 355 1, 678 fied 35,550 3,555 1,828

As has been pomted out previously, the condensation At times we havefound a tendency for an insoluble mass to form or at least to obtainincipient cross-linking or gelling even when the molal ratio is in theorder of 2 moles of resin to one of diepoxide. We have found thisreaction may produce other products, including, for example, a productwhich may be indicated thus in light of what has been said previously:

[=(Amine) CH (Resin) [Oxyalkylated(Amine) CH (Resin)] When a diglycidylether is employed one would obviously obtain compounds in which twomolecules of the kind described immediately preceding are united in amanner comparable to that previously described, which may be indicatedthus:

Bil

l""' 'l Oxyalkylated(Amine)CHz(Resin) Likewise, it is obvious that thetwo different types of oxyalkylation-susceptible compounds may combineso as to give molecules which may be indicated thus:

l(Amine)CH2(Owalkylated Resin)CH (Aminel) I xyalkylated(Amine)CHl(Resin)Oxyalkylated (Amine) C H; (Amine) w I iAminQCHflQxyalkylatedResinlCElflAminei Oxyalkylateddtmine)CHKAmine) D. G. E.

I l Oxyalkylated (Amine) CH (Amine) Actually, the product obtained byreaction with a diglycidyl ether could show considerably greatercomplexity due to the fact that, as previously pointed out, the

condensate reaction probably does not yield a hundred percent condensatein absence of other byproducts. All this simply emphasizes one faot,.'toWit, that there is no 'suitable method of characterizing the finalreaction product except in terms of method of manufacture.

PART 9 v Conventional demulsifying agents employed in the treatment ofoil field emulsions are used as such, or after dilution with anysuitable solvent, such as water, petroleum hydrocarbons, such asbenzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc.Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethylalcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexylalcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneoussolvents such aspine oil, carbon tetrachloride, sulfur dioxide extractobtained in the refining of petroleum, etc., may be employed asdiluents. Similarly, the material or materials employed as the de--Inulsifying agent of our process may be admixed with one or more of thesolvents customarily used in con-. nection with conventional demusifyingagents. Moreover, said material or materials may beused alone or in 38admixture with other suitable well-known classes of demulsifyi-ngagents.

It is Well known that conventional demulsifying agents may be used in awater-soluble form, or in an oil-soluble, form, or in a form exhibitingboth oiland water-solubility. Sometimes they may be used in a form whichexhibits relatively limited oil-solubility. However, since suchreagentsare frequently used in a ratio of l to 10,000 or 1 to 20,000, or 1 to30,000, or even 1 to 40,000, or 1 to 50,000 as in desalting practice,such an apparent insolubility in oil and Water is not significantbecause said reagents undoubtedly have solubility within suchconcentrations. This same fact is true in regard to the material ormaterials of our invention when employed as demulsifyingagents.

The materials of our invention, when employed as treating ordemulsifying agents, are used in the conventional way, well known to theart, described, for example, in Patent 2,626,929, dated January 27,1953, Part 3, and reference is made thereto for a description ofoonventional procedures of demulsifying, including batch, continuous,and down-the-hole demulsification, the process essentially involvingintroducing a small amount of demul'sifier into a large amount ofemulsion with adequateadmixture with or without the application of heat,and allowing the mixture to stratify.

In many instances the oxyalkylated products herein specified asdemulsifiers can be conveniently used without dilution. However, aspreviously noted, they may be diluted as; desired with any suitablesolvent. For instance, by mixing -pa1ts by weight of an oxyalkylatedderivative, for example, the product of Example 3e with 15 parts byweight of xylene and 10 parts by weight of isopropyl alcohol, anexcellent demulsifier is obtained. Selection of the solvent will vary,depending upon the the solubility characteristics of the oxyalkylatedproduct, and of course will be dictated in part by economicconsiderations, i. e., cost.

As noted above, the products herein described may be used not only indiluted form, but also may he used admixed with some other chemicaldemulsifier. A mixture which illustrates such combination is thefollowing:

Oxyalkylated derivative, for example, the product of Example 3e, 20%;

A cyclohexylamine salt of a polypropylated naphthalene monosulfonicacid, 24%;

An ammonium salt of a polypropylated naphthalene monosulfonic acid, 24%;

A sodium salt of oil-soluble mahogany petroleum sulfonie acid, 12%; 1

A high-boiling aromatic petroleum solvent, 15%;

Isopropyl alcohol, 5%.

The above proportions are all weight percents.

PART 10 The products, compounds, or the like, herein described can beemployed for various purposes and particularly for the resolution ofpetroleum emulsions of the waterin-oil type as described in detail inPart 9, preceding.

Such products can be reacted with alkylene imines, such as ethyleneimine or propylene imine, to produce cation-active materials. Instead ofan imine one may employ what is a somewhat equivalent material, to wit,a dialkylamino-epoxypropane of the structure wherein R and R" are alkylgroups.

It is not necessary to point out that, after reaction with a reactantofthe kind described which introduces a basic 39 nitrogen atom, theresultant product can be employed for the resolution of emulsions of thewater-in-oil type as described in Part 5, preceding, and also for otherpurposes described hereinafter.

Referring now to the use of the products obtained by reaction with apolyepoxide and certain specified oxyalkylated products obtained in themanner described in Part 7, preceding, it is to be noted that inaddition to their use in the resolution of petroleum emulsions they maybe used as emulsifying agents for oils, fats, and waxes, as ingredientsin insecticide compositions, or as detergents and wetting agents in thelaundering, scouring, drying, tanning and mordantiug industries. Theymay also be used for preparing boring or metal-cutting oils and cattledips, as metal pickling inhibitors, and for pharmaceutical purposes.

Not only do these oxyalkylated derivatives have utility as such but theycan serve as initial materials for more complicated reactions of thekind ordinarily requiring a hydroxyl radical. This includesesterification, etherization, etc.

The oxyalkylated derivatives may be used as valuable additives tolubricating oils, both those derived from pctroleum and syntheticlubricating oils. Also, they can be used as additives to hydraulic brakefluids of the aqueous and non-aqueous types. They may be used inconnection with other processes where they are injected into an oil orgas Well for purpose of removing a mud sheath, increasing the ultimateflow of fluid from the surrounding strata, and particularly in secondaryrecovery operations using aqueous flood waters. These derivatives alsoare suitable for use in dry cleaners soaps.

More specifically, such products, depending on the nature of the initialresin, the particular monoepoxide selected and the ratio of monoepoxideto resin, together with the particular polyepoxide employed, result in avariety of materials which are useful as Wetting agents or surfacetension reducing agents; as detergents, emulsifiers or dispersingagents; as additives for lubricants, both of the natural petroleum typeand the synthetic type, as additives in the flotation of ores, and attimes as aids in chemical reactions insofar that demulsification isproduced between the insoluble reactants. Furthermore, such products canbe used for a variety of other purposes, including use as corrosioninhibitors, defoamers, asphalt additives, and at times even in theresolution of oil-in-Water emulsions. They serve at times as mutualsolvents promoting a homogeneous system from two otherwise insolublephases.

The products herein described can be reacted with polycarboxy acids,such as phthalic acid or anhydride, maleic acid or anhydride, diglycolicacid, and various tricarboxy and tetracarboxy acids so as to yieldacylated derivatives, particularly if one employs one mole of thepolycarboxy acid for each reactive hydroxyl radical present in the finalpolyepoxide-treated product. Thus, one obtains a comparatively largemolecule in which there is a plurality of carboxyl radicals. Such acidicfractional esters are suitable for the resolution of petroleum emulsionsof the water-in-oil type as herein described.

Having thus described our invention What we claim as new and desire tosecure by Letters Patent is:

l. A three-step manufacturing process involving (1) condensation; (2)oxyalkylation with a monoepoxide; and (3) oxyalkylation with apolyepoxide containing at least two 1,2-epoxy rings; said firstmanufacturing step being a method of (A) condensing (a) a fusible,nonoxygenated organic solvent-soluble, water-insoluble, phenol-aldehyderesin having an average molecular weight corresponding to at least 3 andnot over 6 phenolic nuclei per resin molecule; said resin beingdifunctional only in regard to methylol-forming reactivity; said resinbeing derived by reaction between a difunctional monohydric phenol andan aldehyde having not over 8 carbon atoms and reactive toward saidphenol; said resin being in which R is a saturated aliphatic hydrocarbonradical having at least 4 and not more than 24 carbon atoms andsubstituted in the 2,4,6 position; (b) a basic noniiydroxylatedpolyamine having at least one secondary amino group and having up to 32carbon atoms in any radical attached to any amino nitrogen atom, andwith the further proviso that the polyamine be free from any jl .ryamino radical, any substituted imidazoline radical, and any substitutedtetrahydropyrimidine radical; and (0) formaldehyde; said condensationreaction being c0nducted at a temperature sufficiently high to eliminateWater and below the pyrolytic point of the reactants and resultants ofreaction; and with the proviso that the resinous condensation productresulting from the process be heat-stable; followed as a second step by(B) oxyalkylation by means of an alpha-beta alkylene oxide having notmore than 4 carbon atoms and selected from the class consisting ofethylene oxide, propylene oxide, butylene oxide, glycide andmethylglycide; and then completing the reaction by a third step of (C)reacting said oxyalkylated resin condensate with a phenolic polyepoxidefree from reactive functional groups other than 1,2- epoxy and hydroxylgroups and cogenerically associated compounds formed in the preparationof said polyepoxides; said epoxides being monomers and low molalpolymers not exceeding the tetramers; said polyepoxides being selectedfrom the class consisting of (an) compounds where the phenolic nucleiare directly joined without an intervening bridge radical and (bb)compounds containing a radical in which 2 phenolic nuclei are joined bya divalent radical selected from the class consisting of ketone residuesformed by the elimination of the ketonic oxygen atom, and aldehyderesidues obtained by the elimination of the aldehyde oxygen atom, thedivalent radical the divalent radical, the divalent sulfone radical, anddivalent monosulfide radical S--, the divalent radical -CH SCH,, and thedivalent disulfide radical SS; said phenolic portion of the polyepoxidebeing obtained from a phenol of the structure in which R, R", and R'represent a member of the class consisting of hydrogen and saturatedhydrocarbon substituents of the aromatic nucleus, said substituentmember having not over 18 carbon atoms; with the further proviso thatsaid reactive monoepoxide-oxyalkylated resin condensates and arylpolyepoxides be members of the class consisting of non-thermosettingorganic solvent-soluble liquids and solids melting below the point ofpyrolysis; with the added proviso that the reaction product be a memberof the class of solvent-soluble liquids and solids melting below thepoint of pyrolysis; said reaction between the monoepoxide-oxyalkylatedresin condensate and aryl polyepoxide be conducted below the pyrolyticpoint of the reactants and the resultants of reaction; and with thefinal proviso that the ratio of

1. A THREE-STEP MANUFACTURING PROCESS INVOLVING (1) CONDENSATION; (2)OXYALKYLATION WITH A MONOEPOXIDE; AND (3) OXYALKYLATION WITH APOLYEPOXIDE, CONTAINING AT LEAST TWO 1,2-EPOXY RINGS; SAID FIRSTMANUFACTURING STEP BEING A METHOD OF (A) CONDENSING (A) A FUSIBLE,NONOXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, PHENOL-ALDEHYDERESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDIN G TO AT LEAST 3AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEINGDIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESINBEING DERIVED BY REACTION BETWEREN A DIFUNCTIONAL MONOHYDRIC PHENOL ANDAN ALDEHYDE HAVING NSOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAIDPHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OFTRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA